Organic polymer having epoxy-and/or oxetanyl-containing silicon group at the end and process for producing the same

ABSTRACT

An organic polymer is provided which has an end structure expressed by general formula (1): 
                         
In the formula, R 1  represents an alkyl group having a carbon number in the range of 1 to 20, an aryl group having a carbon number in the range of 6 to 20, an aralkyl group having a carbon number in the range of 7 to 20, or a triorganosiloxy group expressed by (R′) 3 SiO—. R 2  represents an alkyl group having a carbon number in the range of 1 to 20, an aryl group having a carbon number in the range of 6 to 20, an aralkyl group having a carbon number in the range of 7 to 20, an alkoxy group having a carbon number in the range of 1 to 20, or a triorganosiloxy group expressed by (R′) 3 SiO—. X represents a monovalent organic group having an epoxy group and/or an oxetanyl group. m represents an integer in the range of 0 to 20. n represents an integer of 1, 2, or 3.

TECHNICAL FIELD

The present invention relates to structurally novel polymers havingepoxy- and/or oxetanyl-containing silicon groups at their ends, and to aprocess for producing the same.

BACKGROUND ART

Since epoxy groups have superior reactivity, various types of epoxygroup-containing polymers, which are prepared by introducing epoxygroups into various types of polymer, have been developed. In theprocess of epoxidizing an olefin with a peroxide or the like tointroduce an epoxy group, however, the resulting polymer is negativelyaffected by oxidation, and it is disadvantageously difficult toselectively introduce an epoxy group into the end of a polymer and tomake it polyfunctional. Moreover, in some production processes,byproducts must be removed. In particular, a process disclosed inJapanese Unexamined Patent Application Publication No. 3-56505, which isa technique of the foregoing processes, and the structure of theresulting epoxy group-containing polymers may cause oxidationdegradation as mentioned above, or cause an adverse effect to reactivitydue to the steric hindrance around the epoxy group of the resultingpolymer. Thus, epoxy group-containing polymers produced by such knownprocesses do not necessarily have satisfactory physical properties forvarious applications.

It is broadly known that organic polymers each have their owncharacteristics. In particular, saturated hydrocarbon polymers whosemain chain skeleton comprises a polymer selected from the groupconsisting of polyisobutylene, hydrogenated polyisoprene, hydrogenatedpolybutadiene, and their copolymers have high weather resistance, highheat resistance, low gas permeability, superior flexibility, and othercharacteristics. On the other hand, oxyalkylene polymers have superiorcompatibility with other polymers, flexibility, and advantageouslow-temperature characteristics.

Various types of polymers have been developed which are prepared byintroducing hydrolyzable groups, unsaturated groups, hydrosilyl groups,or the like into the ends of the saturated hydrocarbon polymers or theoxyalkylene polymers. However, these polymers disadvantageously requirewater and heating for being cured, and are also disadvantageous instorage stability.

Accordingly, polymers prepared by selectively introducing epoxy groupsinto the ends of various types of organic polymer have been highlydemanded, and a simple production process has also been desired whichprevents the polymers from deteriorating due to the introduction of theepoxy groups and which does not require purification and other steps inassociation with generation of byproducts.

SUMMARY OF THE INVENTION

The object of the present invention is to provide novel organic polymershaving an epoxy- and/or oxetanyl-containing silicon group at their ends,prepared by selectively introducing the epoxy- and/oroxetanyl-containing silicon group into the end of various types oforganic polymers, and a process for producing the organic polymers.

The inventors of the present invention have conducted intensive researchto overcome the above-described disadvantages. As a result, they havefound that a polymer having a specific epoxy- and/or oxetanyl-containingsilicon group exhibits superior physical properties, and haveaccomplished the present invention.

A first invention relates to an organic polymer having at its end thestructure expressed by general formula (1):

(In the formula, R¹ represents an alkyl group having a carbon number inthe range of 1 to 20, an aryl group having a carbon number in the rangeof 6 to 20, an aralkyl group having a carbon number in the range of 7 to20, or a triorganosiloxy group expressed by (R′)₃SiO—. R² represents analkyl group having a carbon number in the range of 1 to 20, an arylgroup having a carbon number in the range of 6 to 20, an aralkyl grouphaving a carbon number in the range of 7 to 20, an alkoxy group having acarbon number in the range of 1 to 20, or a triorganosiloxy groupexpressed by (R′)₃SiO—. If the number of R¹s or R²s is at least two,they may be the same or different. R′ represents a monovalenthydrocarbon group having a carbon number in the range of 1 to 20, thethree R′s may be the same or different. X represents a monovalentorganic group having an epoxy group and/or an oxetanyl group. If thenumber of X is at least two, they may be the same or different. mrepresents an integer in the range of 0 to 20, and n represents aninteger of 1, 2, or 3.)

A second invention relates to an organic polymer having at its end thestructure expressed by general formula (2):

(In the formula, R¹, R², and m are the same as above. R³ represents adivalent organic group having a carbon number in the range of 1 to 20and containing at least one constituent atom selected from the groupconsisting of hydrogen, oxygen, and nitrogen.)

A third invention relates to an organic polymer having at its end thestructure expressed by general formula (3):

(In the formula, R¹, R², and m are the same as above. R⁴ represents adivalent organic group having a carbon number in the range of 1 to 20and containing at least one constituent atom selected from the groupconsisting of hydrogen, oxygen, and nitrogen.)

A fourth invention relates to an organic polymer having at its end thestructure expressed by general formula (4):

(In the formula, R¹, R², and m are the same as above. R⁵ represents adivalent organic group having a carbon number in the range of 1 to 20and containing at least one constituent atom selected from the groupconsisting of hydrogen, oxygen, and nitrogen.)

In the organic polymer of the first invention, preferably, at least oneX has the structure expressed by the following formula:

In another preferred form of the organic polymer of the first invention,at least one X has the structure expressed by the following formula:

In any one of the foregoing inventions, preferably, the main chainskeleton of the organic polymer comprises a saturated hydrocarbonpolymer selected from the group consisting of polyisobutylene,hydrogenated polyisoprene, hydrogenated polybutadiene, and theircopolymers.

In another preferred form of any one of the foregoing inventions, themain chain skeleton of the organic polymer comprises an oxyalkylenepolymer.

In further preferred form of any one of the foregoing inventions, theorganic polymer is produced by an addition reaction of an organicpolymer having an unsaturated group at its end with a hydrosilanecompound having an epoxy group and/or an oxetanyl group. Alternatively,in any one of the foregoing inventions, the organic polymer may beproduced by an exchange reaction of a hydrolyzable group between anorganic polymer having a hydrolyzable silyl group at its end and acompound having at least one epoxy and/or oxetanyl group and onehydroxyl group in its molecule.

A fifth invention relates to a process for producing the organic polymerof any one of the foregoing inventions. The process performs an additionreaction of an organic polymer having an unsaturated group at its endwith a hydrosilane compound having an epoxy group and/or an oxetanylgroup. Another invention relates to a process for producing the organicpolymer of any one of the foregoing inventions. The process performs anexchange reaction of a hydrolyzable group between an organic polymerhaving a hydrolyzable silyl group at its end and a compound having atleast one epoxy and/or oxetanyl group and one hydroxyl group in itsmolecule.

The present invention will now be further described in detail.

DETAILED DISCLOSURE OF INVENTION

An organic polymer having at its end an epoxy- and/oroxetanyl-containing silicon group of the present invention can exhibit asuperior curing property because of the presence of the epoxy- and/oroxetanyl-containing silicon group at the end of the molecular chain.Also, the polymer exhibits its own characteristics depending on the typeof organic polymer main chain constituting the skeleton of the polymer.The main chain skeleton of the organic polymer is not particularlylimited. For example, commonly known organic polymers are used, such asacrylic polymers, polyester polymers, saturated hydrocarbon polymers,and oxyalkylene polymers.

The end structure of the organic polymer of the present invention isexpressed by general formula (1):

In the formula, X represents a monovalent organic group having an epoxygroup and/or an oxetanyl group. X is not particularly limited as long asit is an organic group having an epoxy group and/or an oxetanyl group,and it may have a nitrogen atom, a halogen atom, or other atoms inaddition to hydrogen, carbon, and oxygen atoms. X may have an organicgroup having an ether structure in addition to the epoxy group and/orthe oxetanyl group. Preferably, X is an organic group having a carbonnumber in the range of 1 to 30, more preferably 1 to 20, and still morepreferably 1 to 10. If the number of Xs is at least two, they may be thesame or different.

R¹ represents an alkyl group having a carbon number in the range of 1 to20, an aryl group having a carbon number in the range of 6 to 20, anaralkyl group having a carbon number in the range of 7 to 20, or atriorganosiloxy group expressed by (R′)₃SiO—. R² represents an alkylgroup having a carbon number in the range of 1 to 20, an aryl grouphaving a carbon number in the range of 6 to 20, an aralkyl group havinga carbon number in the range of 7 to 20, an alkoxy group having a carbonnumber in the range of 1 to 20, or a triorganosiloxy group expressed by(R′)₃SiO—. Among these, preferred are alkyl groups having a carbonnumber in the range of 1 to 20 or the phenyl group, and more preferredare alkyl groups having a carbon number in the range of 1 to 6 and thephenyl group, from the viewpoint of reactivity and availability. mrepresents an integer in the range of 0 to 20, and n represents aninteger of 1, 2, or 3. The epoxy group and/or the oxetanyl group may bea common epoxy and/or oxetanyl group, or a cyclic epoxy and/or oxetanylgroup.

Preferably, the end structure of the organic polymer is expressed bygeneral formula (2) from the viewpoint of reactivity of the epoxy group.More preferably, the structure is expressed by general formula (3) or(4) from the viewpoint of ease of production, availability of rawmaterial, and reactivity.

In this formula, R¹, R², and m are the same as above, and R³ representsa divalent organic group having a carbon number in the range of 1 to 20,preferably 1 to 10, and containing at least one constituent atomselected from the group consisting of hydrogen, oxygen, and nitrogen.Specifically, R³ may be a hydrocarbon group or an organic group havingan ether structure.

In this formula, R¹, R², and m are the same as above, and R⁴ representsa divalent organic group having a carbon number in the range of 1 to 20,preferably 1 to 10, and containing at least one constituent atomselected from the group consisting of hydrogen, oxygen, and nitrogen.Specifically, R⁴ may be a hydrocarbon group or an organic group havingan ether structure.

In this formula, R¹, R², and m are the same as above, and R⁵ representsa divalent organic group having a carbon number in the range of 1 to 20,preferably 1 to 10, and containing at least one constituent atomselected from the group consisting of hydrogen, oxygen, and nitrogen.Specifically, R⁵ may be a hydrocarbon group or an organic group havingan ether structure.

The main chain skeleton of the organic polymer of the present inventionis not limited to the above-described structure. If the main chainskeleton comprises a saturated hydrocarbon polymer selected from thegroup consisting of polyisobutylene, hydrogenated polyisoprene,hydrogenated polybutadiene, and their copolymers, or an oxyalkylenepolymer, the cured product prepared from such an organic polymerexhibits rubber elasticity. The combined use of such an organic polymerand an epoxy resin, such as bisphenol A, gives weather resistance andflexibility to the polymer. In particular, saturated hydrocarbonpolymers are also given a low gas permeability.

The saturated hydrocarbon polymers substantially contain no unsaturatedcarbon-carbon bond except aromatic rings, and whose examples includepolyethylene, polypropylene, polyisobutylene, hydrogenatedpolybutadiene, and hydrogenated polyisoprene.

The polymer constituting the saturated hydrocarbon polymer main chainskeleton may be prepared by: (1) homopolymerizing or copolymerizing acomponent or components essentially consisting of an olefinic compoundhaving a carbon number in the range of 1 to 6, such as ethylene,propylene, 1-butene, and isobutylene; or (2) homopolymerizing orcopolymerizing a diene or dienes, such as butadiene and isoprene, orcopolymerizing a diene and the above-mentioned olefinic compound andsubsequently hydrogenating the copolymer. In particular, isobutylenepolymers and hydrogenated polybutadiene polymers are suitable becausethey facilitate the introduction of functional groups into their ends,the molecular weight is easy to control, and the number of terminalfunctional groups can be increased. Among these, particularly preferredare isobutylene polymers. This is because isobutylene polymers are easyto handle due to their liquid feature or fluidity, and contain nounsaturated carbon-carbon bond except aromatic rings in the main chainand, accordingly, do not require to be hydrogenated. Furthermore, theyhave excellent weather resistance.

The isobutylene polymer may comprise monomer units consisting ofisobutylene, or may further contain a monomer unit copolymerizable withisobutylene in an amount of, preferably, 50% by weight or less, morepreferably 30% by weight or less, and particularly preferably 10% byweight or less.

Such monomer units include olefins having a carbon number in the rangeof 4 to 12, vinyl ethers, aromatic vinyl compounds, vinyl silanes, andallyl silanes. Examples of the copolymerization components include1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene,4-methyl-1-pentene, hexene, vinylcyclohexene, methyl vinyl ether, ethylvinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene,dimethylstyrene, monochlorostyrene, dichlorostyrene, β-pinene, indene,vinyltrichlorosilane, vinylmethyldichlorosilane,vinyldimethylchlorosilane, vinyldimethylmethoxysilane,vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane,divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane,trivinylmethylsilane, tetravinylsilane, allyltrichlorosilane,allylmethyldichlorosilane, allyldimethylchlorosilane,allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane,diallyldimethoxysilane, diallyldimethylsilane,γ-methacryloyloxypropyltrimethoxysilane, andγ-methacryloyloxypropylmethyldimethoxysilane.

The hydrogenated polybutadiene polymer and other saturated hydrocarbonpolymers may also contain other monomer units in addition to the mainconstituent monomer unit, as in the foregoing isobutylene polymer.

The saturated hydrocarbon polymer, particularly isobutylene polymer orhydrogenated polybutadiene polymer, preferably has a number averagemolecular weight of about 500 to 50,000. In particular, a hydrocarbonpolymer having a number average molecular weight of about 1,000 to20,000 and exhibiting a liquid feature or fluidity is more preferablefrom the viewpoint of ease of handling.

The main chain structure of the oxyalkylene polymer comprises repeatingunits expressed by —R⁶—O—, wherein R⁶ represents a divalent organicgroup having a carbon number in the range of 1 to 20. The oxyalkylenepolymer may be a homopolymer, which comprises a single type of repeatingunit, or a copolymer, which comprises at least two types of repeatingunit. The main chain may further have a branch structure.

Examples of R⁶ include —CH₂CH₂—, —CH(CH₃)CH₂—, —CH(C₂H₅)CH₂—,—C(CH₃)₂CH₂—, and —CH₂CH₂CH₂CH₂—. Among these, preferred is—CH(CH₃)CH₂—.

The main chain skeleton of the oxyalkylene polymer is prepared by, forexample, ring-opening polymerization of monoepoxide with a startingmaterial in the presence of a catalyst.

Exemplary starting material include dihydric alcohols, such as ethyleneglycol, propylene glycol, butanediol, hexamethylene glycol, methallylalcohol, bisphenol A, hydrogenated bisphenol A, neopentyl glycol,polybutadienediol, diethylene glycol, triethylene glycol, polyethyleneglycol, polypropylene glycol, polypropylenetriol, polypropylenetetraol,dipropylene glycol, glycerin, trimethylolmethane, trimethylolpropane,and pentaerythritol; polyhydric alcohols; and oligomers having ahydroxyl group.

Examples of the monoepoxide include alkylene oxides, such as ethyleneoxide, propylene oxide, α-butylene oxide, β-butylene oxide, hexeneoxide, cyclohexene oxide, styrene oxide, and α-methylstyrene oxide;alkyl glycidyl ethers, such as methyl glycidyl ether, ethyl glycidylether, isopropyl glycidyl ether, and butyl glycidyl ether; allylglycidyl ethers; and aryl glycidyl ethers.

The polyoxyalkylene polymer is synthesized by, for example, apolymerization in the presence of an alkaline catalyst, such as KOH, apolymerization in the presence of a transition metal compound-porphyrincomplex, such as a complex obtained from a reaction between an organicaluminium compound and a porphyrin, as disclosed in Japanese UnexaminedPatent Application Publication No. 61-215623, a polymerization in thepresence of a compound metal cyanide complex catalyst as disclosed in,for example, Japanese Examined Patent Application Publication Nos.46-27250 and 59-15336, a polymerization in the presence of a cesiumcatalyst, and a polymerization in the presence of a phosphazenecatalyst. However, the synthesis of the polyoxyalkylene polymer is notparticularly limited to these polymerizations. Among these, preferred isthe polymerization in the presence of a compound metal cyanide complexcatalyst, from the viewpoint of ease of preparation of a less coloredpolymer having a high molecular weight.

Alternatively, the main chain skeleton of the polyoxyalkylene polymermay be prepared by chain elongation or the like of a hydroxyl-terminatedoxyalkylene polymer with a difunctional or higher functional halogenatedalkyl, such as CH₂Cl₂ or CH₂Br₂, in the presence of a basic compound,such as KOH, NaOH, KOCH₃, or NaOCH₃.

The main chain skeleton of the oxyalkylene polymer may contain othercomponents, such as urethane bond components, as long as such componentsdo not negatively affect the characteristics of the oxyalkylene polymer.

The process for introducing the epoxy- and/or oxetanyl-containingsilicon group having the structure expressed by any one of generalformulas (1) to (4) into an end of an organic polymer is notparticularly limited. However, preferred introduction is performed byaddition of an epoxy-and/or oxetanyl-containing hydrosilane compound toan unsaturated group, or hydrolyzable group exchange reaction between anorganic polymer having a hydrolyzable silyl group at its end and acompound having at least one epoxy group and/or oxetanyl group and onehydroxyl group in its molecule because these processes do not causedegradation resulting from oxidation in the introduction nor requirepurification by, for example, deoxidation after the introduction.Preferred compounds having at least one epoxy group and/or oxetanylgroup and one hydroxyl group in its molecule include2,3-epoxy-1-propanol, 3-ethyl-3-(hydroxymethyl)oxetane, and glycerindiglycidyl ether because these compounds are easily available.

The introduction by addition reaction of the hydrosilane compound can beconducted by either of the processes of: synthesizing an unsaturatedgroup-terminated organic polymer and subsequently adding amonohydrosilane compound having an epoxy group and/or an oxetanyl group;adding a hydrosilane compound having at least two hydrosilyl groups inits molecule into an end of an organic polymer and subsequently addingan epoxy and/or oxetane compound having an unsaturated group, such as anallyl group, into an unreacted hydrosilyl group. Preferably, the formerprocess is adopted from the viewpoint of ease of production, selectivityin reaction, and easy control of introduction quantity of the epoxygroup and/or the oxetanyl group.

In order to obtain a polymer having a specific end structure in thepresent invention, a hydrosilane compound expressed by general formula(5) may be used.

In the formula, R¹, R², X, m, and n are the same as in general formula(1).

In particular, it is preferable to use a hydrosilane compound expressedby general formula (6) from the viewpoint of high reactivity of theterminal epoxy group, and more preferable to use a hydrosilane compoundexpressed by general formula (7) or (8) from the viewpoint of ease ofproduction, availability, and high reactivity.

In this formula, R¹, R², R³, and m are the same as above.

In this formula, R¹, R², R⁴, and m are the same as above.

In this formula, R¹, R², R⁵, and m are the same as above.

The hydrosilane compound can be synthesized by a known syntheticprocess. For synthesis, for example, a polysiloxane compound havinghydrosilyl groups at its both ends is subjected to addition reactionwith an epoxy compound having an unsaturated group by hydrosilylation,as described in Journal of Polymer Science Part A, Polymer Chemistry,Vol. 31, 2563–2572 (1993) or Vol. 31, 2729–2737 (1993).

In the hydrosilane compound, R¹ is more preferably methyl from theviewpoint of availability. Examples of such compounds are listed belowwhile being listed in the foregoing literatures.

The unsaturated group-terminated organic polymer can be synthesized by agenerally known process without problems. For example, ahalogen-terminal polymer prepared by living cationic polymerization maybe dehydrohalogenated with a metal alkoxide, or allyltrimethylsilane orthe like may be allowed to react in the presence of titaniumtetrachloride or the like to introduce an unsaturated group. Also, acompound having an unsaturated bond may be reacted with a hydroxyterminal to form an ether bond, ester bond, urethane bond, carbonatebond, or the like, thereby introducing an unsaturated group.

For example, in the formation of an unsaturated group-terminated polymerfrom a polymer having a hydroxy terminal, the hydroxy terminal isconverted into an oxymetal group, such as —ONa or —OK, followed byreaction with an unsaturated group-containing organic compound expressedby general formula (9):CH₂═CH—R⁷—Y  (9), orgeneral formula (10):CH₂═C(R⁸)—R⁷—Y  (10)(in the formulas, R⁷ represents a divalent organic group having a carbonnumber in the range of 1 to 20, R⁸ represents a hydrocarbon group havinga carbon number of 10 or less, and Y represents a halogen atom).

To convert the hydroxy terminal into an oxymetal group, the terminal isreacted with, for example, an alkali metal, such as Na or K, a metalhydride, such as NaH, metal alkoxide, such as NaOCH₃, or an alkalihydroxide, such as NaOH or KOH.

Examples of the unsaturated group-containing compound expressed bygeneral formula (9) or (10) include: CH₂═CH—CH₂—Cl, CH₂═CH—CH₂—Br,CH₂═CH—C₂H₄—Cl, CH₂═CH—C₂H₄—Br, CH₂═CH—C₃H₆—Cl, CH₂═CH—C₃H₆—Br,CH₂═C(CH₃)—CH₂—Cl, CH₂═C(CH₃)—CH₂—Br, CH₂═C(CH₂CH₃)—CH₂—Cl,CH₂═C(CH₂CH₃)—CH₂—Br, CH₂═C(CH₂CH(CH₃)₂)—CH₂—Cl, andCH₂═C(CH₂CH(CH₃)₂)—CH₂—Br. Among these, preferred are CH₂═CH—CH₂—Cl andCH₂═C(CH₃)—CH₂—Cl, particularly from the viewpoint of reactivity.

The unsaturated group may be introduced by another process using anisocyanate compound, a carboxylic acid, an epoxy compound, or the likehaving a CH₂═CH—CH₂— group, a CH₂═C(CH₃)—CH₂— group, or the like.

The above-mentioned hydrosilylation is preferably performed by areaction between an unsaturated group-terminated organic polymer and ahydrosilyl compound in the presence of a Group VIII transition metalcatalyst.

An advantageous VIII transition metal catalyst is selected from metalcomplex catalysts containing Group VIII transition metal elements, suchas platinum, rhodium, cobalt, palladium, and nickel. Examples of such acatalyst include H₂PtCl₆.6H₂O, platinum-vinylsiloxane complexes,platinum-olefin complexes, Pt metal, RhCl(PPh₃)₃, RhCl₃, Rh/Al₂O₃,RuCl₃, IrCl₃, FeCl₃, PdCl₂.2H₂O, and NiCl₂. Preferably, any one ofH₂PtCl₆.6H₂O, platinum-vinylsiloxane complexes, and platinum-olefincomplexes is used from the viewpoint of hydrosilylation reactivity.Platinum-vinylsiloxane complexes are particularly preferable because theinduction period of reaction is short.

In addition to these compounds, AlCl₃, TiCl₄, and benzoyl peroxide andother radical initiators may be used as the hydrosilylation catalyst.

The temperature of the hydrosilylation is selected from the viewpoint ofreaction rate, provided such a side reaction as negatively affects thepolymer does not easily occur. The temperature is generally in the rangeof 10 to 150° C., preferably 20 to 120° C., more preferably 40 to 100°C. For adjusting the reaction temperature or the viscosity of thereaction system, or for the reason of other necessity, a solvent may beused, such as benzene, toluene, xylene, tetrahydrofuran, methylenechloride, pentane, hexane, or heptane.

In order to accelerate the hydrosilylation, a process may be applied,such as reactivation of catalyst with oxygen, as disclosed in JapaneseUnexamined Patent Application Publication No. 8-283339, or addition ofsulfur.

In order to prevent oxidation of the organic polymer, the reactionsolvent, the plasticizer in the system, and the like, thehydrosilylation may be performed in the presence of an antioxidant.

For the measurement of the percentage of introduction of the epoxy-and/or oxetanyl-containing silicon group, various methods can beapplied. At present, the percentage can be accurately obtained bycomparing the integral obtained from NMR spectra of the end into whichthe epoxy- and/or oxetanyl-containing silicon group is introduced tothat of the end into which such groups are not introduced.

The process for producing a saturated hydrocarbon polymer having anepoxy- and/or oxetanyl-containing silicon group at its end will now bedescribed in detail.

An isobutylene polymer having and epoxy group and/or an oxetanyl groupat its end of the present invention may be produced with use of anend-functional, preferably all-end-functional, isobutylene polymerprepared by polymerization called the inifer process (cationicpolymerization using a specific compound called an inifer, serving as aninitiator and a chain transfer agent). For the introduction of an epoxy-and/or oxetanyl-containing silicon group into the polymer, for example,an unsaturated group-terminated polyisobutylene is prepared bydehalogenating the end-functional polymer or introducing an unsaturatedgroup into a polymer as disclosed in Japanese Unexamined PatentApplication Publication No. 63-105005, and then the polyisobutylene issubjected to addition reaction with the epoxy- and/oroxetanyl-containing hydrosilane compound expressed by general formula(6), (7), or (8) by hydrosilylation in the presence of a platinumcatalyst.

As for hydrogenated polybutadiene polymer, for example, the hydroxyterminal of a hydroxyl-terminated hydrogenated polybutadiene polymer isconverted into an oxymetal group, such as —ONa or —OK, followed by areaction with an unsaturated group-containing compound expressed bygeneral formula (9) or (10). Thus, an unsaturated group-terminatedhydrogenated polybutadiene polymer can be obtained.

The product unsaturated group-terminated hydrogenated polybutadienepolymer has substantially the same molecular weight as the startingmaterial hydroxyl-terminated hydrogenated polybutadiene polymer. For apolymer having a higher molecular weight, the starting material is firstreacted with a polyvalent organic halogen compound containing at leasttwo halogens, such as methylene chloride, bis(chloromethyl)benzene, orbis(chloromethyl)ether, in its molecule before the reaction with theorganic halogen compound expressed by general formula (9) or (10), sothat the molecular weight can be increased. Then, the product is reactedwith the organic halogen compound expressed by general formula (9) or(10) to yield a higher molecular weight hydrogenated polybutadienepolymer having an olefin group at its end.

The introduction of the epoxy- and/or oxetanyl-containing silicon groupinto the unsaturated group-terminated hydrogenated polybutadiene polymeris performed by an addition reaction with a hydrosilane compound in thepresence of a platinum catalyst, as in the case of isobutylene polymer.

Saturated hydrocarbon polymers containing substantially no unsaturatedbond except aromatic rings provide coatings having superior weatherresistance to coatings formed of known rubber polymers, such asunsaturated bond-containing organic polymers. Also, since such polymersare hydrocarbon polymers, they have low gas permeability and high waterresistance, accordingly providing advantageously less gas-permeablecoatings.

A process for preparing the oxyalkylene polymer having an epoxy and/oroxetanyl-containing silicon group at its end is not particularlylimited. The oxyalkylene polymer is, for example, obtained byhydrosilylation of the above-described unsaturated group-terminatedoxyalkylene polymer with the monohydrosilane compound having an epoxy-and/or oxetanyl-containing silicon group expressed by general formula(6), (7), or (8).

For the production of the unsaturated group-terminated oxyalkylenepolymer, the following process can be applied. In, for example, the caseof introducing an unsaturated group with an ether bond, the hydroxyterminal of an oxyalkylene polymer is converted into a metaloxy group—OM (M represents Na, K, or the like), and subsequently reacted with theunsaturated group-containing compound expressed by general formula (9)or (10), as above.

For the introduction of an epoxy group and/or an oxetanyl group into thepolymer end by hydrolyzable group exchange reaction, a hydrolyzablesilyl-terminated organic polymer is subjected to a hydrolyzable groupexchange reaction with a compound having at least one epoxy and/oroxetanyl group and one hydroxyl group in its molecule.

The hydrolyzable silyl group of the hydrolyzable silyl-terminatedorganic polymer is not particularly limited, but is typically expressedby the groups expressed by general formula (11), for example:—[SiR¹ ₂O]_(m)Si(R² _(3-n))Z_(n)  (11)(In the formula, R¹, R², m, and n are the same as above. Z represents ahydroxyl group or a hydrolyzable group, and if the number of Zs is twoor more, they may be the same or different.)

The hydrolyzable group expressed by Z is not particularly limited, andany known hydrolyzable group can be used. Exemplary hydrolyzable groupsinclude the hydrogen atom, halogen atoms, and alkoxy, acyloxy,ketoximate, amino, amido, acid amido, aminoxy, mercapto, and alkenyloxygroups. Among these, preferred are alkoxy groups, such as methoxy,ethoxy, propoxy, and isopropoxy, from the viewpoint of gentlehydrolyzability and ease of handling.

If at least two of the hydrolyzable or hydroxyl groups are present in areactive silicon group, they may be the same or different.

Preferably, the reactive silicon group is expressed by general formula(12) because of availability.—Si(R² _(3-n))Z_(n)  (12)(In the formula, R², Z and n are the same as above.) The process forproducing the hydrolyzable silyl-terminated organic polymer is notparticularly limited, and the unsaturated group-terminated organicpolymer and a hydrosilane compound expressed by following generalformula (13) may be subjected to the above-described addition reaction.H—[SiR¹ _(2]) _(m)Si(R² _(3-n))Z_(n)  (13)(In the formula, R¹, R², Z, m, and n are the same as above.)

In particular, from the viewpoint of availability, the hydrosilanecompound is preferably expressed by general formula (14):H—Si(R² _(3-n))Z_(n)  (14)(In the formula, R², Z, m and n are the same as above.)

Examples of the compound expressed by general formulas (13) and (14)include silane halides, such as trichlorosilane, methyldichlorosilane,dimethylchlorosilane, phenyldichlorosilane,trimethylsiloxymethylchlorosilane, and1,1,3,3-tetramethyl-1-bromodisiloxane; alkoxysilanes, such astrimethoxysilane, triethoxysilane, methyldiethoxysilane,methyldimethoxysilane, phenyldimethoxysilane,trimethylsiloxymethylmethoxysilane, and trimethylsiloxydiethoxysilane;acyloxysilanes, such as methyldiacetoxysilane, phenyldiacetoxysilane,triacetoxysilane, trimethylsiloxymethylacetoxysilane, andtrimethylsiloxydiacetoxysilane; ketoximate silanes, such asbis(dimethylketoximate)methylsilane,bis(cyclohexylketoximate)methylsilane,bis(diethylketoximate)trimethylsiloxysilane,bis(methylethylketoximate)methylsilane, and tris(acetoximate)silane; andalkenyloxysilanes, such as methylisopropenyloxysilane. Among these,preferred are alkoxysilanes. Particularly preferred alkoxy groupsinclude methoxy, ethoxy, propoxy, and isopropoxy groups.

The compound having at least one epoxy and/or oxetanyl group and onehydroxyl group in its molecule to be reacted with the above-describedhydrolyzable silyl-terminated organic polymer is not particularlylimited, but is preferably a secondary or primary compound having ahydroxyl group from the viewpoint of reactivity.

Examples of the compound having at least one epoxy and/or oxetanyl groupand one hydroxyl group in its molecule are expressed by general formula(15).W—OH  (15)(W represents a monovalent organic group having an epoxy group and/or anoxetanyl group.)

Examples of such compounds include 2,3-epoxy-1-propanol,3-ethyl-3-hydroxymethyloxetane, and glycerin diglycidyl ether, from theviewpoint of availability. Among these, preferred are2,3-epoxy-1-propanol and 3-ethyl-3-hydroxymethyloxetane, which areprimary alcohols.

The quantity of the compound is not particularly limited. However, inorder to promote the exchange reaction, at least 1 mole equivalent ofthe compound is used relative to the hydrolyzable group of thehydrolyzable silyl-terminated organic polymer.

The exchange reaction of the hydrolyzable group can be performed by areaction between the above-described hydrolyzable silyl-terminatedorganic polymer and the above-described compound having at least oneepoxy and/or oxetanyl group and one hydroxyl group in its molecule inthe presence of a transesterification catalyst.

Examples of the transesterification catalyst include alkali metalalkoxides, Sn compounds, Ti compounds, Zn compounds, Ba compounds, andconventionally used highly alkaline compounds. Suitabletransesterification catalysts include dimethyltin neodecanoate,dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate,dibutyltin dioctate, zinc naphthenate, cobalt naphthenate, zincoctylate, tin octylate, cobalt octylate, diisooctyl mercaptoacetate,zirconium naphthenate, zirconium octylate, tetrabutyl titanate,tetraisopropyl titanate, barium hydroxide monohydrate, and other organicmetal catalysts. In particular, the transesterification catalyst ispreferably selected from among tetraisopropyl titanate, barium hydroxidemonohydrate, and alkoxides, such as sodium methoxide.

The quantity of the transesterification catalyst to be used is notparticularly limited, but is generally in the range of 50 to 100,000ppm, and preferably 50 to 3,000 relative to the organic polymer.

In the transesterification, a solvent may be further used. Examples ofthe solvent include, but not particularly limited to, aliphatichydrocarbons, such as pentane, cyclopentane, hexane, cyclohexane,heptane, octane, and nonane; aromatic hydrocarbons, such as benzene,toluene, and xylene; and fluorine-, chlorine-, or bromine-substitutedaliphatic or aromatic hydrocarbons, such as perchloroethylene andbromobenzene. At least two nonpolar solvents may be used in combination.

The quantity of the solvent is not limited, but 100 parts by weight ofthe polymer may contain 0 to 100 parts by weight of the solvent.

The transesterification can be promoted by devolatilization of theproduct. For devolatilization, known processes in the art can beapplied. Any devolatilization process may be adopted in the presentinvention. For example, the devolatilization is performed by heating,heating and decompression, using a rotatory evaporator, a thin-filmstripper, or a wiped film evaporator, or a combination of these methods.Preferably, the devolatilization is performed by heating the product toa temperature of 50 to 150° C. under a reduced pressure of about 20 to100 Torr.

The organic polymer having at its end an epoxy- and/oroxetanyl-containing silicon group of the present invention is a novelpolymer prepared by introducing an epoxy- and/or oxetanyl-containingsilicon group selectively into its end, and can be synthesized in aproduction process preventing degradation of its main chain and otheradverse effects. The resulting polymer can be cured independently by aknown reaction of the epoxy group and/or the oxetanyl group, and can beused for modification of conventionally used epoxy cured product. Thesecured products are expected to exhibit characteristics derived from themain chain of the polymer.

The organic polymer having at its end an epoxy- and/oroxetanyl-containing silicon group of the present invention can be curedby, but not particularly limited to, reacting the epoxy group and/or theoxetanyl group with a common curing agent for epoxy- and/oroxetanyl-containing compounds. Examples of the curing agent includeamine-based curing agents, acid-based curing agents, borontrifluoride-amine complex curing agents, and photo-cation curing agents.These agents can be used in common processes.

In particular, a photo-curing reaction is preferably adopted because itallows short-time curing. For the photo-curing reaction, a cationicphoto-initiator may be used. Suitable cationic photo-initiators includeonium salts, diaryliodonium sulfonates, triarylsulfonium sulfonates,diaryliodonium boronates, triarylsulfonium boronates, andphoto-initiators disclosed in Japanese Unexamined Patent ApplicationPublication Nos. 5-117311, 11-49791, or 2000-226396.

The organic polymer having at its end an epoxy- and/oroxetanyl-containing silicon group of the present invention may containanother polymer, a filler, a reinforcer, other additives, and acatalyst, if necessary, so that the resulting polymer can beadvantageously used as adhesive, paint, sealant compositions,waterproofing material, spraying material, molding material, andinjection rubber.

Best Mode for Carrying Out the Invention

The present invention will be further described in detail with referenceto examples, but the invention is not limited by the examples.

EXAMPLE 1 Synthesis of Allyl-Terminated Isobutylene Polymer

A 2 L pressure-resistant glass vessel was equipped with a three-waystopcock and purged with nitrogen. Into the vessel were added, with asyringe, 138 mL of ethylcyclohexane (dried by being allowed to stand atleast overnight together with molecular sieve 3A), 1,012 mL of toluene(dried by being allowed to stand at least overnight together withmolecular sieve 3A), and 8.14 g (35.2 mmol) of1,4-bis(α-chloroisopropyl)benzene.

A pressure-resistant glass liquefied sampling tube equipped with aneedle valve, containing 254 mL (2.99 mol) of isobutylene monomer wasjoined to the three-way stopcock. Then, the polymerization vessel wascooled in a dry ice/ethanol bath of −70° C., and subsequentlydepressurized with a vacuum pump. After introducing the isobutylenemonomer into the polymerization vessel from the liquefied gas samplingtube with the needle valve open, nitrogen was introduced into the vesselthrough one way of the three-way stopcock, and thus the pressure in thevessel was increased to normal pressure. Then, 0.387 g (4.15 mmol) of2-methylpyridine was added. Subsequently, 4.90 mL (44.7 mmol) oftitanium tetrachloride was added to initiate polymerization. After areaction time of 70 minutes, 9.65 g (13.4 mmol) of allyltrimethylsilanewas added to introduce an allyl group into an end of the polymer. Aftera reaction time of 120 minutes, the reaction solution was washed with200 mL of water four times, and the solvent was evaporated to yield anallyl-terminated isobutylene polymer.

The yield of the product polymer was calculated, and the Mn and theMw/Mn was determined by GPC. The end structure was determined by 300 MHz¹H-NMR in which the intensities of resonance signals of protons from theconstituent structures (protons of the starting material: 6.5 to 7.5ppm; peaks of terminal allyl groups of the polymer (4.97 ppm: ═CH₂, 5.79ppm: —CH═C) were measured and compared. The ¹H—NMR analysis wasperformed in carbon tetrachloride/heavy acetone with Varian Gemini 300(300 MHz for ¹H).

The GPC was performed with a liquid delivery system Waters LC Module 1and a column Shodex K-804. The molecular weight was defined as arelative molecular weight to a polystyrene standard. The results ofpolymer analysis were: Mn =5,800; Mw/Mn =1.35; and Fn(v) =2.04 (numberof allyl groups per molecule of an aromatic ring being the residue ofthe starting material).

(Introduction of epoxy-containing silicon group into polymer terminal)

A 300 mL three-neck flask was charged with 100 g of the allyl-terminatedpolyisobutylene polymer and 2 g of toluene, and equipped with a stirrerhaving a vacuum seal, a three-way stopcock, and a ball cock. Thereaction system was heated to 180° C. and stirred, and the water andhydrochloric acid in the reaction system were removed with a vacuum pumpfor two hours.

After cooling the reaction system to 100° C., 0.05 g of3,5-di-tert-butyl-4-hydroxytoluene, 21.6 μL ofplatinum-1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex (3% by weightsolution in toluene, in terms of platinum), and 11.1 μL of 1% sulfursolution in toluene were dripped, and the mixture was sufficientlystirred.

Into the reaction mixture was slowly dripped, from a dripping tube, 9.13g of an epoxy group-containing monohydrosilane having the followingstructure prepared by a reaction of an allyl glycidyl ether withtetramethyldisiloxane. The mixture was stirred for 2 hours in aircontaining 6% of oxygen.

The progress of the reaction was monitored by ¹H-NMR, and confirmed byreduction or disappearance of the peak heights of terminal allyl groups(4.97 ppm:═CH₂, 5.79 ppm: —CH═C) and reduction of the peak height of thehydrosilyl group (Si—H, 4.65 ppm) of the dripped epoxy group-containingmonohydrosilane.

The ¹H-NMR analysis of the reaction product showed that the peaks of theabove-mentioned allyl groups of the original allyl-terminated polymerand hydrosilane completely disappeared. Thus, it was confirmed that anisobutylene polymer having at a desired end an epoxy-containing silicongroup expressed by the following formula was obtained:

EXAMPLE 2 Synthesis of Allyl-terminated Oxypropylene Polymer

A starting material polypropylene glycol having a number averagemolecular weight of 2,000 was polymerized with propylene oxide in thepresence of a zinc hexacyanocobaltate-glyme complex catalyst to yield apolypropylene glycol having a number average molecular weight of 10,000.Then, CH₃ONa (solution in methanol) was added in an amount of 1.2equivalents per terminal hydroxyl group of the resulting polypropyleneglycol, and the terminal was converted into a metaloxy group while themethanol was removed under reduced pressure. Into the reaction system,1.3 equivalents of 3-chloro-1-propene was added. After a reaction,byproduct salts were removed by demineralization to yield anallyl-terminated oxypropylene polymer.

(Introduction of Epoxy-containing Silicon Group into Polymer Terminal)

A 300 mL three-neck flask was charged with 100 g of the allyl-terminatedoxypropylene polymer and 2 g of hexane, and equipped with a stirrerhaving a vacuum seal, a three-way stopcock, and a ball cock. Thereaction system was heated to 90° C. and stirred, and the water in thereaction system was removed with a vacuum pump for two hours byazeotropic dehydration.

Then, 4.10 μL of platinum-1,1,3,3-tetramethyl-1,3-divinyldisiloxanecomplex (3% by weight solution in toluene, in terms of platinum) wasdripped, and the mixture was sufficiently stirred. Into the reactionsystem, 4.52 g of the same epoxy group-containing monohydrosilane as inExample 1 was slowly dripped in an atmosphere of nitrogen, and themixture was stirred for 2 hours.

The progress of the reaction was monitored by ¹H-NMR, and confirmed byreduction or disappearance of the peak heights of terminal allyl groups(4.97 ppm: ═CH₂, 5.79 ppm: —CH═C) and reduction of the peak height ofthe hydrosilyl group (Si—H, 4.65 ppm) of the dripped epoxygroup-containing monohydrosilane.

The ¹H-NMR analysis of the reaction product showed that the peaks of theabove-mentioned allyl groups of the original allyl-terminated polymerand hydrosilane completely disappeared. Thus, it was confirmed that anoxyalkylene polymer having at its end an epoxy-containing silicon groupexpressed by the following formula was obtained:

EXAMPLE 3

A 300 mL three-neck flask was charged with 100 g of the allyl-terminatedpolyisobutylene polymer and 2 g of toluene, and equipped with a stirrerhaving a vacuum seal, a three-way stopcock, and a ball cock. Thereaction system was heated to 180° C. and stirred, and the water andhydrochloric acid in the reaction system were removed with a vacuum pumpfor two hours.

After cooling the reaction system to 100° C., 0.05 g of3,5-di-tert-butyl-4-hydroxytoluene, 21.6 μL ofplatinum-1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex (3% by weightsolution in toluene, in terms of platinum), and 11.1 μL of 1% sulfursolution in toluene were dripped, and the mixture was sufficientlystirred.

Into the reaction mixture was slowly dripped, from a dripping tube, 9.50g of an epoxy group-containing monohydrosilane having the followingstructure prepared by a reaction of 1,2-epoxy-4-vinylcyclohexane withtetramethyldisiloxane. The mixture was stirred for 2 hours in aircontaining 6% of oxygen.

The progress of the reaction was monitored by ¹H-NMR, and confirmed byreduction or disappearance of the peak heights of terminal allyl groups(4.97 ppm: ═CH₂, 5.79 ppm: —CH═C) and reduction of the peak height ofthe hydrosilyl group (Si—H, 4.65 ppm) of the dripped epoxygroup-containing monohydrosilane.

The ¹H-NMR analysis of the reaction product showed that the peaks of theabove-mentioned allyl groups of the original allyl-terminated polymerand hydrosilane completely disappeared. Thus, it was confirmed that anisobutylene polymer having at a desired end an epoxy-containing silicongroup expressed by the following formula was obtained:

EXAMPLE 4 Synthesis of Hydrolyzable Silyl Group-containing Polymer

A 300 mL three-neck flask was charged with 100 g of the allyl-terminatedpolyisobutylene polymer and 2 g of toluene, and equipped with a stirrerhaving a vacuum seal, a three-way stopcock, and a ball cock. Thereaction system was heated to 180° C. and stirred, and the water andhydrochloric acid in the reaction system were removed with a vacuum pumpfor two hours.

After cooling the reaction system to 100° C., 0.05 g of3,5-di-tert-butyl-4-hydroxytoluene, 21.6 μL ofplatinum-1,1,3,3-tetramethyl-1,3-divinyldisiloxane complex (3% by weightsolution in toluene, in terms of platinum), and 11.1 μL of 1% sulfursolution in toluene were dripped,-and the mixture was sufficientlystirred.

Into the reaction system, 5.86 g of methyldimethoxysilane was slowlydripped from a dripping tube, and the mixture was stirred for 2 hours inair containing 6% of oxygen. Then, excess methyldimethoxysilane wasremoved under reduced pressure to yield an isobutylene polymer having atits end a hydrolyzable group having the following structure:

(Hydrolyzable Group Exchange Reaction)

A 500 mL flask equipped with a Dean-Stark separator was charged with 100g of the alkoxysilyl-terminated polyisobutylene polymer and 100 g oftoluene. Subsequently, 14.4 g of 3-ethyl-3-hydroxymethyloxetane and 200μL of tetraisopropoxy titanate were added. The mixture was heated to 70°C. to react for 16 hours while being stirred. After the reaction,toluene and excess 3-ethyl-3-hydroxymethyloxetane were removed underreduced pressure.

The progress of the reaction was monitored by ¹H-NMR, and confirmed byreduction or disappearance of the peak height of the terminal methoxygroup (3.5 ppm: —CH₃).

The ¹H-NMR analysis of the reaction product showed that the averagenumber of introduced terminal 3-ethyl-3-hydroxymethyloxetanyl groups was1.5. Thus, it was confirmed that an isobutylene polymer having at adesired end an oxetanyl-containing silicon group expressed by thefollowing formula was obtained:

INDUSTRIAL APPLICABILITY

The present invention provides polymers prepared by selectively andquantitatively introducing epoxy- and/or oxetanyl-containing silicongroups into ends of various types of organic polymer, and a simpleprocess for producing the polymers which prevents the introduction ofthe epoxy groups from oxidizing or negatively affecting the polymers andwhich does not require purification and other steps in association withgeneration of byproducts.

The resulting organic polymer having an epoxy- and/oroxetanyl-containing silicon group at its end has superior reactivity,and its cured product and known cured products modified with the organicpolymer can exhibit the characteristics of the main chain skeleton ofthe polymer. Thus, the organic polymer of the present invention can beadvantageously used in various industrial applications.

1. An organic polymer having an end structure expressed by generalformula (1):

(wherein R¹ represents an alkyl group having a carbon number in therange of 1 to 20, an aryl group having a carbon number in the range of 6to 20, an aralkyl group having a carbon number in the range of 7 to 20,or a triorganosiloxy group expressed by (R′)₃SiO—; R² represents analkyl group having a carbon number in the range of 1 to 20, an arylgroup having a carbon number in the range of 6 to 20, an aralkyl grouphaving a carbon number in the range of 7 to 20, an alkoxy group having acarbon number in the range of 1 to 20, or a triorganosiloxy groupexpressed by (R′)₃SiO—; if the number of R¹s or R²s is at least two,they may be the same or different; R′ represents a monovalenthydrocarbon group having a carbon number in the range of 1 to 20 and thethree R′s may be the same or different; X represents a monovalentorganic group having an epoxy group and/or an oxetanyl group, and if thenumber of Xs is at least two, they may be the same or different; mrepresents an integer in the range of 0 to 20; and n represents aninteger of 1, 2, or 3), and wherein the main chain skeleton of theorganic polymer comprises a saturated hydrocarbon polymer selected fromthe group consisting of polyisobutylene, hydrogenated polyisoprene,hydrogenated polybutadiene, and copolymers thereof.
 2. An organicpolymer having an end structure expressed by general formula (2):

(wherein R¹ represents an alkyl group having a carbon number in therange of 1 to 20, an aryl group having a carbon number in the range of 6to 20, an aralkyl group having a carbon number in the range of 7 to 20,or a triorganosiloxy group expressed by (R′)₃SiO—; R² represents analkyl group having a carbon number in the range of 1 to 20, an arylgroup having a carbon number in the range of 6 to 20, an aralkyl grouphaving a carbon number in the range of 7 to 20, an alkoxy group having acarbon number in the range of 1 to 20, or a triorganosiloxy groupexpressed by (R′)₃SiO—; if the number of R¹s or R²s is at least two,they may be the same or different; R′ represents a monovalenthydrocarbon group having a carbon number in the range of 1 to 20 and thethree R′s may be the same or different; R³ represents a divalent organicgroup having a carbon number in the range of 1 to 20 and containing atleast one constituent atom selected from the group consisting ofhydrogen, oxygen, and nitrogen; and m represents an integer in the rangeof 0 to 20), and wherein the main chain skeleton of the organic polymercomprises a saturated hydrocarbon polymer selected from the groupconsisting of polyisobutylene, hydrogenated polyisoprene, hydrogenatedpolybutadiene, and copolymers thereof.
 3. An organic polymer having anend structure expressed by general formula (3):

(wherein R¹ represents an alkyl group having a carbon number in therange of 1 to 20, an aryl group having a carbon number in the range of 6to 20, an aralkyl group having a carbon number in the range of 7 to 20,or a triorganosiloxy group expressed by (R′)₃SiO—; R² represents analkyl group having a carbon number in the range of 1 to 20, an arylgroup having a carbon number in the range of 6 to 20, an aralkyl grouphaving a carbon number in the range of 7 to 20, an alkoxy group having acarbon number in the range of 1 to 20, or a triorganosiloxy groupexpressed by (R′)₃SiO—; if the number of R¹s or R²s is at least two,they may be the same or different; R′ represents a monovalenthydrocarbon group having a carbon number in the range of 1 to 20 and thethree R′s may be the same or different; R⁴ represents a divalent organicgroup having a carbon number in the range of 1 to 20 and containing atleast one constituent atom selected from the group consisting ofhydrogen, oxygen, and nitrogen; and m represents an integer in the rangeof 0 to 20), and wherein the main chain skeleton of the organic polymercomprises a saturated hydrocarbon polymer selected from the groupconsisting of polyisobutylene, hydrogenated polyisoprene, hydrogenatedpolybutadiene, and copolymers thereof.
 4. An organic polymer having anend structure expressed by general formula (4):

(wherein R¹ represents an alkyl group having a carbon number in therange of 1 to 20, an aryl group having a carbon number in the range of 6to 20, an aralkyl group having a carbon number in the range of 7 to 20,or a triorganosiloxy group expressed by (R′)₃SiO—; R² represents analkyl group having a carbon number in the range of 1 to 20, an arylgroup having a carbon number in the range of 6 to 20, an aralkyl grouphaving a carbon number in the range of 7 to 20, an alkoxy group having acarbon number in the range of 1 to 20, or a triorganosiloxy groupexpressed by (R′)₃SiO—; if the number of R¹s or R²s is at least two,they may be the same or different; R′ represents a monovalenthydrocarbon group having a carbon number in the range of 1 to 20 and thethree R′s may be the same or different; R⁵ represents a divalent organicgroup having a carbon number in the range of 1 to 20 and containing atleast one constituent atom selected from the group consisting ofhydrogen, oxygen, and nitrogen; and m represents an integer in the rangeof 0 to 20), and wherein the main chain skeleton of the organic polymercomprises a saturated hydrocarbon polymer selected from the groupconsisting of polyisobutylene, hydrogenated polyisoprene, hydrogenatedpolybutadiene, and copolymers thereof.
 5. The organic polymer accordingto claim 1, wherein at least one X has a structure expressed by thefollowing formula:


6. The organic polymer according to claim 1, wherein at least one X hasa structure expressed by the following formula:


7. The organic polymer according to claim 1, wherein the organic polymeris produced by an addition reaction of an organic polymer having anunsaturated group at an end thereof with a hydrosilane compound havingan epoxy group and/or an oxetanyl group.
 8. A process for producing theorganic polymer as set forth in claim 1, the process comprising the stepof performing an addition reaction of an organic polymer having anunsaturated group at an end thereof with a hydrosilane compound havingan epoxy group and/or an oxetanyl group.
 9. The organic polymeraccording to claim 1, wherein the organic polymer is produced by anexchange reaction of a hydrolyzable group between an organic polymerhaving a hydrolyzable silyl group at an end thereof and a compoundhaving at least one epoxy and/or oxetanyl group and one hydroxyl groupin one molecule thereof.
 10. A process for producing the organic polymeras set forth in claim 1, the process comprising the step of performingan exchange reaction of a hydrolyzable group between an organic polymerhaving a hydrolyzable silyl group at an end thereof and a compoundhaving at least one epoxy and/or oxetanyl group and one hydroxyl groupin one molecule thereof.